Pathways towards large-scale implementation of CO2 capture and storage: A case study for the Netherlands

We sketch four possible pathways how carbon dioxide capture and storage (CCS) (r)evolution may occur in the Netherlands, after which the implications in terms of CO₂ stored and avoided, costs and infrastructural requirements are quantified. CCS may play a significant role in decarbonising the Dutch energy and industrial sector, which currently emits nearly 100 Mt CO₂/year. We found that 15 Mt CO₂ could be avoided annually by 2020, provided some of the larger gas fields that become available the coming decade could be used for CO₂ storage. Halfway this century, the mitigation potential of CCS in the power sector, industry and transport fuel production is estimated at maximally 80–110 Mt CO₂/year, of which 60–80 Mt CO₂/year may be avoided at costs between 15 and 40 €/t CO₂, including transport and storage. Avoiding 30–60 Mt CO₂/year by means of CCS is considered realistic given the storage potential represented by Dutch gas fields, although it requires planning to assure that domestic storage capacity could be used for CO₂ storage. In an aggressive climate policy, avoiding another 50 Mt CO₂/year may be possible provided that nearly all capture opportunities that occur are taken. Storing such large amounts of CO₂ would only be possible if the Groningen gas field or large reservoirs in the British or Norwegian part of the North Sea will become available.     

Chilled ammonia process for CO2 capture

The chilled ammonia process absorbs the CO₂ at low temperature (2–10 °C). The heat of absorption of carbon dioxide by ammonia is significantly lower than for amines. In addition, degradation problems can be avoided and a high carbon dioxide capacity is achieved. Hence, this process shows good perspectives for decreasing the heat requirement. However, a scientific understanding of the processes is required. The thermodynamic properties of the NH₃–CO₂–H₂O system were described using the extended UNIQUAC electrolyte model developed by Thomsen and Rasmussen in a temperature range from 0 to 110 °C and pressure up to 100 bars. The results show that solid phases consisting of ammonium carbonate and bicarbonate are formed in the absorber. The heat requirements in the absorber and in the desorber have been studied. The enthalpy calculations show that a heat requirement for the desorber lower than 2 GJ/ton CO₂ can be reached.     

New correlations predict aqueous solubility and density of carbon dioxide

In this paper, new correlations for predicting density and the solubility of carbon dioxide in pure water as well as the aqueous sodium chloride solutions are developed, where using the generated interaction parameters, the solubility model is applied to correlate the carbon dioxide solubilities in aqueous solutions for temperatures between 300 and 400 K and pressures from 50 to 700 bar. The correlation developed for predicting density of carbon dioxide accurately works for pressures between 25 and 700 bar and temperatures between 293 and 433 K. The results have been compared with the reported data and it was found that there is a good agreement between the prediction results and observed values.     

Paper and biomass for energy?: The impact of paper recycling on energy and CO2 emissions

The pulp and paper industry is placed in a unique position as biomass used as feedstock is now in increasingly high demand from the energy sector. Increased demand for biomass increases pressure on the availability of this resource, which might strengthen the need for recycling of paper. In this study, we calculate the energy use and carbon dioxide emissions for paper production from three pulp types. Increased recycling enables an increase in biomass availability and reduces life-cycle energy use and carbon dioxide emissions. Recovered paper as feedstock leads to lowest energy use (22 GJ/t) and CO₂ emissions (−1100 kg CO₂/t) when biomass not used for paper production is assumed to be converted into bio-energy. Large differences exist between paper grades in e.g. electricity and heat use during production, fibre furnish, filler content and recyclability. We found large variation in energy use over the life-cycle of different grades. However, in all paper grades, life-cycle energy use decreases with increased recycling rates and increased use of recovered fibres. The average life-cycle energy use of the paper mix produced in The Netherlands, where the recycling rate is approximately 75%, is about 14 GJ/t. This equals CO₂ savings of about 1 t CO₂/t paper if no recycled fibres would be used.     

Assessment of basin-scale hydrologic impacts of CO2 sequestration,Illinois basin

Idealized, basin-scale sharp-interface models of CO₂ injection were constructed for the Illinois basin. Porosity and permeability were decreased with depth within the Mount Simon Formation. Eau Claire confining unit porosity and permeability were kept fixed. We used 726 injection wells located near 42 power plants to deliver 80 million metric tons of CO₂/year. After 100 years of continuous injection, deviatoric fluid pressures varied between 5.6 and 18 MPa across central and southern part of the Illinois basin. Maximum deviatoric pressure reached about 50% of lithostatic levels to the south. The pressure disturbance (>0.03 MPa) propagated 10–25 km away from the injection wells resulting in significant well–well pressure interference. These findings are consistent with single-phase analytical solutions of injection. The radial footprint of the CO₂ plume at each well was only 0.5–2 km after 100 years of injection. Net lateral brine displacement was insignificant due to increasing radial distance from injection well and leakage across the Eau Claire confining unit. On geologic time scales CO₂ would migrate northward at a rate of about 6 m/1000 years. Because of paleo-seismic events in this region (M5.5–M7.5), care should be taken to avoid high pore pressures in the southern Illinois basin.     

A 13C NMR investigation of CO2 absorption and desorption in aqueous 2,2′-iminodiethanol and N-methyl-2,2′-iminodiethanol

The carbon dioxide capture and release from aqueous 2,2′-iminodiethanol (DEA) and N-methyl-2,2′-iminodiethanol (MDEA) have been investigated by means of ¹³C NMR spectroscopy. We have designed two experimental procedures using a gas mixture containing 12% (v/v) CO₂ in N₂ or air and 0.667 M aqueous solutions of DEA and MDEA. To understand the CO₂–amine reaction equilibria, separate experiments of CO₂ absorption (at 293, 313 and 333 K) and desorption (at boiling temperature, room pressure) were carried out. The ¹³C NMR analysis has allowed us to establish: (1) the percentage of CO₂ stored in solution as HCO₃^?, CO₃^2? and DEA carbamate; (2) the formation of DEA carbamate as a function of absorption temperature and time; (3) the slower decomposition of DEA carbamate than that of bicarbonate. In the experiments planned to test the reuse of the regenerated amines, the absorbent solution was continuously circulated in a closed cycle while it was absorbing CO₂ in the absorber (set at 293 K) and simultaneously regenerating amine in the desorber (set at 388 K). After the equilibrium has been reached (13 h), the CO₂ absorption efficiency is comprised between 84.0% (DEA) and 82.6% (MDEA) and the average amine regeneration efficiency ranges between 69.6% (DEA) and 78.2% (MDEA). Additionally, MDEA is more stable towards thermal degradation than DEA.     

Natural analogue of the rise and dissolution of liquid CO2 in the ocean

The behavior of natural carbon dioxide (CO₂) droplets (8–10 mm in diameter) were observed in a seafloor hydrothermal system at the Okinawa Trough. The natural CO₂ droplet contain 95–98% of CO₂, 2–3% of H₂S, and other gas species. The ascending CO₂ droplets were tracked by a remotely operated vehicle (ROV), and depth, temperature, salinity, pH and partial pressure of CO₂ (pCO₂) in seawater near the CO₂ droplets were measured during droplet ascent by a conductivity-temperature-depth sensor (CTD) and in situ pH/pCO₂ sensor. The visual images of the rising CO₂ droplets were recorded with a high definition television camera on the ROV. A mapping survey (400 m × 400 m; 4 horizontal layers) revealed a dominant distribution of low pH area over the natural CO₂ venting site. The size and rise rate of CO₂ droplets decreased during their ascent in the water column from depths of 1424 to 679 m (a tracking interval of 745 m). The CO₂ droplets dissolved gradually to become small flakes of CO₂ hydrate while rising, and these ascending flakes were found to disappear at 679 m depth. Although a pH as low as 5 was detected just above the liquid CO₂ venting site on the seafloor, no detectable pH depression in the water column ambient to the rising CO₂ droplets was observed. The results of the pH mapping survey showed only localized pH depression over the CO₂ venting site.     

CO2 capture from power plants: Part I. A parametric study of the technical performance based on monoethanolamine

Capture and storage of CO₂ from fossil fuel fired power plants is drawing increasing interest as a potential method for the control of greenhouse gas emissions. An optimization and technical parameter study for a CO₂ capture process from flue gas of a 600 MWe bituminous coal fired power plant, based on absorption/desorption process with MEA solutions, using ASPEN Plus with the RADFRAC subroutine, was performed. This optimization aimed to reduce the energy requirement for solvent regeneration, by investigating the effects of CO₂ removal percentage, MEA concentration, lean solvent loading, stripper operating pressure and lean solvent temperature.Major energy savings can be realized by optimizing the lean solvent loading, the amine solvent concentration as well as the stripper operating pressure. A minimum thermal energy requirement was found at a lean MEA loading of 0.3, using a 40 wt.% MEA solution and a stripper operating pressure of 210 kPa, resulting in a thermal energy requirement of 3.0 GJ/ton CO₂, which is 23% lower than the base case of 3.9 GJ/ton CO₂. Although the solvent process conditions might not be realisable for MEA due to constraints imposed by corrosion and solvent degradation, the results show that a parametric study will point towards possibilities for process optimisation.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

1D and 2D absorption-rate/kinetic modeling and simulation of carbon dioxide absorption into mixed aqueous solutions of MDEA and PZ in a laminar jet apparatus

The kinetics of the reaction between carbon dioxide (CO₂) and mixed solutions of methyldiethanolamine (MDEA) and piperazine (PZ) was investigated experimentally in a laminar jet apparatus. The experimental kinetic data were obtained under no interfacial turbulence and over a temperature range from 313 to 333 K, MDEA/PZ wt% concentration ratios of 27/3, 24/6 and 21/9, and CO₂ loadings from 0.0095 to 0.33 mol CO₂/mol amine. In addition, a new absorption-rate/kinetics model for the kinetics of the mixed of solvents was developed, which takes into account the coupling between chemical equilibrium, mass transfer, and all possible chemical reactions involved in the CO₂ reaction with MDEA/PZ solvent. The partial differential equations of this model were solved by the finite element numerical method (FEM) based on COMSOL software. The obtained experimental kinetics data were used to obtain the kinetic parameters of CO₂ absorption into MDEA/PZ solutions. The reaction-rate constant obtained for PZ blended with MDEA was kPZ = 2.572 × 10¹² exp(?5211/T). The 2D model for the blended amines MDEA/PZ has revealed the concentration profiles of all the species in both the radial and axial directions of the laminar jet which has enabled a better understanding of the correct sequence in which the reaction steps involved in the reactive absorption of CO₂ in aqueous mixed MDEA/PZ solution occur. It also revealed that PZ may be depleted by the time the solvent blend of MDEA/PZ with a loading greater than 0.015 mol/mol amine is exposed to CO₂ from the top of the laminar jet absorber.     

Hydrate formation during CO2 transport: Predicting water content in the fluid phase in equilibrium with the CO2-hydrate

In order to evaluate the risk of hydrate formation in CO₂ transport one has to be able to predict the water content in the fluid phase in equilibrium with the CO₂-hydrate. A literature review has identified some knowledge gaps, for example, there are no results available at temperatures lower than 243.15 K (?30 °C); and none of the models found in literature predicts the water content with high accuracy. A model based on equality of water fugacity in fluid and hydrate phase is presented here and used for the predictions of water content in equilibrium with hydrates. Although this model gives better accuracy in the overall temperature and pressure ranges of measurements than the models found in the literature, it is not accurate enough to satisfy the requirements of CO₂ transport. The simulation results also show that it is possible to form hydrate at low water content, such as x_w = 50 vppm, if temperature is low enough. In order to verify the results and improve the model accuracy further, more experimental data in a larger temperature and pressure region are required.     

Carbon dioxide capture with concentrated,aqueous piperazine

Concentrated, aqueous piperazine (PZ) has been investigated as a novel amine solvent for carbon dioxide (CO₂) absorption. The CO₂ absorption rate of aqueous PZ is more than double that of 7 m MEA and the amine volatility at 40 °C ranges from 11 to 21 ppm. Thermal degradation is negligible in concentrated, aqueous PZ up to a temperature of 150 °C, a significant advantage over MEA systems. Oxidation of concentrated, aqueous PZ is appreciable in the presence of copper (4 mM), but negligible in the presence of chromium (0.6 mM), nickel (0.25 mM), iron (0.25 mM), and vanadium (0.1 mM). Initial system modeling suggests that 8 m PZ will use 10–20% less energy than 7 m MEA. The fast mass transfer and low degradation rates suggest that concentrated, aqueous PZ has the potential to be a preferred solvent for CO₂ capture.     

Experimental investigation of the CO2 sealing efficiency of caprocks

Using a combination of experimental (petrophysical and mineralogical) methods, the effects of high-pressure CO₂ exposure on fluid transport properties and mineralogical composition of two pelitic caprocks, a limestone and a clay-rich marl lithotype have been studied. Single and multiphase permeability tests, gas breakthrough and diffusion experiments were conducted under in situ p/T conditions on cylindrical plugs (28.5 mm diameter, 10–20 mm thickness).The capillary CO₂ sealing efficiency of the initially water-saturated sample plugs was found to decrease in repetitive gas breakthrough experiments on the same sample from 0.74 to 0.41 MPa for the limestone and from 0.64 to 0.43 MPa for the marl. Helium breakthrough experiments before and after the CO₂ tests showed a decrease in capillary threshold (snap-off) pressure from 1.81 to 0.62 MPa for the limestone.Repetitive CO₂ diffusion experiments on the marlstone revealed an increase in the effective diffusion coefficient from 7.8 × 10^?11 to 1.2 × 10^?10 m².Single-phase (water) permeability coefficients derived from steady-state permeability tests ranged between 7 and 56 nano-Darcy and showed a consistent increase after each CO₂ test cycle. Effective gas permeabilities were generally one order of magnitude lower than water permeabilities and exhibit the same trend. XRD measurements performed before and after exposure to CO₂ did not reveal any distinct change in the mineral composition for both samples. Similarly, no significant changes were observed in specific surface areas (determined by BET) and pore-size distributions (determined by mercury injection porosimetry). High-pressure CO₂ sorption experiments on powdered samples revealed significant CO₂ sorption capacities of 0.27 and 0.14 mmol/g for the marlstone and the limestone, respectively.The changes in transport parameters in the absence of detectable mineral alterations may be explained by carbonate dissolution and further precipitation along a pH profile across the sample plug which would not be subject to quantitative mineral alteration.     

Degradation of aqueous piperazine in carbon dioxide capture

Concentrated, aqueous piperazine (PZ) is a novel solvent for carbon dioxide (CO₂) capture by absorption/stripping. One of the major advantages of PZ is its resistance to thermal degradation and oxidation.At 135 and 150 °C, 8 m PZ is up to two orders of magnitude more resistant to thermal degradation than 7 m monoethanolamine (MEA). After 18 weeks at 150 °C, only 6.3% of the initial PZ was degraded, yielding an apparent first order rate constant for amine loss of 6.1 × 10^?9 s^?1. PZ was the most resistant amine tested, with the other screened amines shown in order of decreasing resistance: 7 m 2-amino-2-methyl-1-propanol, 7 m Diglycolamine^®, 7 m N-(2-hydroxyethyl)piperazine, 7 m MEA, 8 m ethylenediamine, and 7 m diethylenetriamine. Thermal resistance allows the use of higher temperatures and pressures in the stripper, potentially leading to overall energy savings.Concentrated PZ solutions demonstrate resistance to oxidation compared to 7 m MEA solutions. Experiments investigating metal-catalyzed oxidation found that PZ solutions were 3–5 times more resistant to oxidation than MEA. Catalysts tested were 1.0 mM iron (II), 4.0–5.0 mM copper (II), and a combination of stainless steel metals (iron (II), nickel (II), and chromium (III)). Inhibitor A reduced PZ degradation catalyzed by iron (II) and copper (II).     

Worst case scenario study to assess the environmental impact of amine emissions from a CO2 capture plant

Use of amines is one of the leading technologies for post-combustion carbon dioxide capture from gas and coal-fired power plants. This study assesses the potential environmental impact of emissions to air that result from use of monoethanol amine (MEA) as an absorption solvent for the capture of carbon dioxide (CO₂). Depending on operation conditions and installed reduction technology, emissions of MEA to the air due to solvent volatility losses are expected to be in the range of 0.01–0.8 kg/tonne CO₂ captured. Literature data for human and environmental toxicity, together with atmospheric dispersion model calculations, were used to derive maximum tolerable emissions of amines from CO₂ capture. To reflect operating conditions with typical and with elevated emissions, we defined a scenario MEA-LOW, with emissions of 40 t/year MEA and 5 t/year diethyl amine (DEYA), and a scenario MEA-HIGH, with emissions of 80 t/year MEA and 15 t/year DEYA. Maximum MEA deposition fluxes would exceed toxicity limits for aquatic organisms by about a factor of 3–7 depending on the scenario. Due to the formation of nitrosamines and nitramines, the estimated emissions of DEYA are close to or exceed safety limits for drinking water and aquatic ecosystems. The “worst case” scenario approach to determine maximum tolerable emissions of MEA and other amines is in particular useful when both expected environmental loads and the toxic effects are associated with high uncertainties.     

CO2 capture from power plants: Part II. A parametric study of the economical performance based on mono-ethanolamine

While the demand for reduction in CO₂ emission is increasing, the cost of the CO₂ capture processes remains a limiting factor for large-scale application. Reducing the cost of the capture system by improving the process and the solvent used must have a priority in order to apply this technology in the future. In this paper, a definition of the economic baseline for post-combustion CO₂ capture from 600 MW_e bituminous coal-fired power plant is described. The baseline capture process is based on 30% (by weight) aqueous solution of monoethanolamine (MEA). A process model has been developed previously using the Aspen Plus simulation programme where the baseline CO₂-removal has been chosen to be 90%. The results from the process modelling have provided the required input data to the economic modelling. Depending on the baseline technical and economical results, an economical parameter study for a CO₂ capture process based on absorption/desorption with MEA solutions was performed.Major capture cost reductions can be realized by optimizing the lean solvent loading, the amine solvent concentration, as well as the stripper operating pressure. A minimum CO₂ avoided cost of € 33 tonne⁻¹ CO₂ was found for a lean solvent loading of 0.3 mol CO₂/mol MEA, using a 40 wt.% MEA solution and a stripper operating pressure of 210 kPa. At these conditions 3.0 GJ/tonne CO₂ of thermal energy was used for the solvent regeneration. This translates to a € 22 MWh⁻¹ increase in the cost of electricity, compared to € 31.4 MWh⁻¹ for the power plant without capture.     

Gas conditioning—The interface between CO2 capture and transport

Gas conditioning is commonly referred to as the required processing for a produced natural gas to achieve transport and sales specifications. In this paper, gas conditioning as the processing required in the interface between CO₂ capture and transport is studied for nine different natural gas fired power plant concepts and three different CO₂ transport processes. Conditioning processes for both pipeline and ship transport are described and an enhanced process for volatile removal is developed. The energy requirement for the conditioning processes is normally between 90 and 120 kWh/tonne CO₂; however, this depends on the pressure and composition of the captured CO₂-rich stream. The loss of CO₂ in the water purge is small for most capture processes. The waste streams from the gas conditioning processes can contain large amounts of CO₂ and should therefore be further processed or reintroduced at an appropriate point upstream in the capture or gas conditioning process if possible. The integration benefit may vary depending on the composition of the CO₂-rich stream. It could be particularly interesting for processes with “innovative reactors” (membranes, sorbents, chemical looping) to integrate CO₂ capture and gas conditioning.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Energy and carbon dioxide intensity of Thailand's steel industry and greenhouse gas emission projection toward the year 2050

The purpose of this article is to study the energy and carbon dioxide intensities of Thailand's steel industry and to propose greenhouse gas emission trends from the year 2011 to 2050 under plausible scenarios. The amount of CO₂ emission from iron and steel production was calculated using the 2006 Intergovernmental Panel on Climate Change (IPCC) guidelines in the boundary of production process (gate to gate). The results showed that energy intensity of semi-finished steel product was 2.84 GJ/t semi-finished steel and CO₂ intensity was 0.37 tCO_2eq/t semi-finished steel. Energy intensity of steel finishing process was 1.86 GJ/t finished steel and CO₂ intensity was 0.16 tCO_2eq/t finished steel. Using three plausible scenarios from Thailand's steel industry, S1: without integrated steel plant (baseline scenario), S2: with a traditional integrated BF–BOF route and S3: with an alternative integrated DR-EAF route; the Greenhouse Gas emissions from the year 2011 to 2050 were projected. In 2050, the CO₂ emission from S1 (baseline scenario) was 4.84 million tonnes, S2 was 21.96 million tonnes increasing 4.54 times from baseline scenario. The CO₂ emission from S3 was 7.12 million tonnes increasing 1.47 times from baseline scenario.     

Carbon dioxide capture and recovery by means of TSA and/or VSA

Experimental work is performed with a 5A zeolite on a small laboratory column with heating from the wall. Carbon dioxide adsorption occurs at atmospheric pressure and different CO₂ concentrations in nitrogen. Comparisons of different methods of desorption by heating, purge and/or vacuum are studied. Desorption by heating only leads to almost pure CO₂ (around 99% purity) and a recovery nearly linear to the heating temperature, ranging from 45% at 130 °C to 79% at 210 °C. Recovery can be subsequently increased with a nitrogen purge to more than 98% but the recovered carbon dioxide is diluted due to the dispersive character of the desorption wave and the operation time is long. Increasing the flow rate decreases the desorption time but has no effect on the purity because the total purge volume remains about the same. Substitution of the purge step with a vacuum step leads to pure CO₂ and almost total recovery. Desorption under vacuum only without heating leads to pure CO₂ (around 99% purity) but limited recovery (85% in the present work).Desorption under vacuum seems to be more simple for large-scale applications. When using a water liquid ring pump, the temperature of the ring must be kept as low as possible to provide a high operating capacity.